WO2011013677A1

WO2011013677A1 - Gas-barrier multilayer film

Info

Publication number: WO2011013677A1
Application number: PCT/JP2010/062642
Authority: WO
Inventors: 高津　洋二; 祐美津曲; 大川　剛; 芳治森原; 修成松田
Original assignee: 東洋紡績株式会社
Priority date: 2009-07-31
Filing date: 2010-07-27
Publication date: 2011-02-03
Also published as: US9605122B2; TWI508858B; EP2460656A1; KR101389222B1; TW201119858A; EP2460656B1; KR20120030579A; US20120128956A1; EP2460656A4; CN102481769B; CN102481769A

Abstract

Provided is a gas-barrier multilayer film which decreases little in gas-barrier properties even through retortion and which suffers no delamination. The gas-barrier multilayer film is characterized by comprising a plastic film and, superposed directly or through other layer on at least one surface thereof in the following order, an inorganic thin film layer and a gas-barrier resin composition layer. The gas-barrier film is further characterized in that the gas-barrier resin composition layer has been formed from a gas-barrier resin composition comprising a gas-barrier resin constituted of an ethylene/vinyl alcohol copolymer, an inorganic lamellar compound, and an additive, that the content of the inorganic lamellar compound in the gas-barrier resin composition is 0.1-9.0 mass%, that the additive is a coupling agent and/or a crosslinking agent, and that the gas-barrier resin composition layer has a thickness of 0.05-0.5 µm.

Description

Gas barrier laminated film

The present invention relates to a gas barrier laminate film having transparency, excellent gas barrier properties against water vapor, oxygen and the like, and suitable as a packaging film for foods, pharmaceuticals and the like. More specifically, the present invention relates to a gas barrier laminate film that can provide good gas barrier properties and adhesion (laminate strength) even by retorting.

Conventionally, a film in which a metal thin film such as aluminum or a thin film of inorganic oxide such as silicon oxide or aluminum oxide is laminated on the surface of a plastic film has been known as a gas barrier film. Especially, the film which laminated | stacked thin films of inorganic oxides, such as a silicon oxide, aluminum oxide, and these mixtures, is transparent and can confirm the content, and is widely used for the food use.

However, these inorganic thin films are liable to generate pinholes and cracks in the thin film formation process, and the inorganic thin film layer cracks and generates cracks in the processing process, so that sufficient gas barrier properties as expected are not obtained. Therefore, as a method for improving such a defect, an attempt has been made to further provide a gas barrier layer on the inorganic thin film. As a gas barrier film of such a method, a gas barrier film (for example, Patent Document 1) in which a resin layer containing an inorganic layered compound having a specific particle diameter and aspect ratio is coated on an inorganic thin film is disclosed.

Many films have also been proposed in which the surface of a plastic film is coated with a resin composition having a high gas barrier property. In the resin composition used for such a film, a method of dispersing a flat form inorganic substance such as an inorganic layered compound in the resin is also known as a method for improving gas barrier properties. For example, on a base film There has been proposed (for example, Patent Document 2) provided with a barrier coat layer comprising an ethylene-vinyl alcohol copolymer, a water-soluble zirconium-based crosslinking agent, and an inorganic layered compound.

However, even with these methods, although improvement in characteristics under boiling and high humidity is recognized, a gas barrier film having a stable quality and satisfactory gas barrier properties after retort and laminate strength can be obtained. The current situation was not.

Japanese Patent No. 3681426 JP 2008-297527 A

The present invention has been made against the background of the problems of the prior art. That is, the object of the present invention is to provide excellent gas barrier properties and interlayer adhesion that can be used for various foods and pharmaceuticals, industrial product packaging applications, solar cells, electronic paper, organic EL elements, semiconductor elements, and the like. It is providing the gas-barrier laminated film which has these. In particular, an object of the present invention is to provide a gas barrier laminated film in which the gas barrier property is hardly lowered even after the retort treatment and delamination does not occur.

The gas barrier laminate film of the present invention that has been able to solve the above-mentioned problems is provided with an inorganic thin film layer and a gas barrier resin composition layer on at least one surface of a plastic film with or without other layers interposed therebetween. The gas barrier resin composition layer is formed from a gas barrier resin composition comprising an ethylene-vinyl alcohol copolymer and a gas barrier resin composition comprising an inorganic layered compound and an additive, and the gas barrier property The content of the inorganic stratiform compound in the resin composition is 0.1% by mass to 9.0% by mass, the additive is a coupling agent and / or a crosslinking agent, and the gas barrier resin composition layer The thickness is 0.05 μm to 0.5 μm.

The inorganic layered compound is preferably smectite. The inorganic thin film layer preferably contains at least an inorganic oxide.

When a coupling agent is used as the additive, the coupling agent is preferably a silane coupling agent having at least one organic functional group. When a crosslinking agent is used as the additive, the crosslinking agent preferably contains a hydrogen bonding group crosslinking agent. In this case, the total content of the additives (coupling agent and / or crosslinking agent) in the gas barrier resin composition is preferably 0.3% by mass to 20% by mass.

It is also a preferred embodiment that an anchor coat layer having a thickness of 0.05 μm to 0.5 μm is provided between the inorganic thin film layer and the gas barrier resin composition layer. The anchor coat agent resin composition for forming the anchor coat layer preferably contains a silane coupling agent having at least one organic functional group. In addition, the amount of the silane coupling agent added to the anchor coat agent resin composition for forming the anchor coat layer is preferably 0.1% by mass to 10% by mass.

According to the present invention, a gas barrier laminate film having excellent gas barrier properties against oxygen and water vapor and having high interlayer adhesion and excellent laminate strength can be obtained. In particular, even if a retort treatment is performed, the gas barrier property and interlayer adhesive force are hardly lowered, and a highly practical gas barrier laminate film suitable for various applications can be obtained. Moreover, it becomes the gas barrier laminated film which is excellent in production stability and is easy to obtain uniform characteristics.

In the gas barrier laminate film of the present invention, an inorganic thin film layer and a gas barrier resin composition layer are laminated in this order with or without other layers on at least one surface of a plastic film. Hereinafter, the gas barrier laminate film of the present invention will be described separately for each layer.

1. Gas barrier resin composition layer The gas barrier resin composition layer is formed from a gas barrier resin composition. The gas barrier resin composition comprises a gas barrier resin made of an ethylene-vinyl alcohol copolymer (hereinafter sometimes referred to as “EVOH”), an inorganic layered compound, and an additive. Hereinafter, individual configurations of the gas barrier resin composition layer will be described.

1-1. Gas barrier resin EVOH that can be used as the gas barrier resin includes, for example, those obtained by saponifying an ethylene-vinyl acetate copolymer. Specific examples of those obtained by saponifying the above-mentioned ethylene-vinyl acetate copolymer include those obtained by saponifying an ethylene-vinyl acetate copolymer obtained by copolymerizing ethylene and vinyl acetate; ethylene and acetic acid Examples thereof include those obtained by saponifying an ethylene-vinyl acetate copolymer obtained by copolymerizing other monomers together with vinyl. In the present invention, a copolymer obtained by copolymerizing ethylene and vinyl acetate, and a copolymer obtained by copolymerizing other monomers together with ethylene and vinyl acetate are collectively referred to as “ethylene-vinyl acetate”. System-based copolymer ".

In the case of an ethylene-vinyl acetate copolymer, the ethylene ratio in the monomer composition before copolymerization is preferably 20 mol% to 60 mol%. When the ethylene ratio is 20 mol% or more, the gas barrier property under high humidity is further improved, and the decrease in the laminate strength after the retort treatment is further suppressed. On the other hand, when the ethylene ratio is 60 mol% or less, the gas barrier properties are further improved. The ethylene-vinyl acetate copolymer preferably has a saponification degree of the vinyl acetate component of 95 mol% or more. When the saponification degree of the vinyl acetate component is 95 mol% or more, the gas barrier properties and oil resistance are improved.

In addition, the EVOH may have a molecular weight cut by treatment with a peroxide or the like so as to improve dissolution stability in a solvent, thereby reducing the molecular weight.
Examples of the peroxide include the following (1) to (7).
(1) H ₂ O ₂
(2) M ₂ O ₂ type (M: Na, K, NH ₄ , Rb, Cs, Ag, Li, etc.)
(3) M′O ₂ type (M ′: Mg, Ca, Sr, Ba, Zn, Cs, Hg, etc.)
(4) R—O—O—R type (R represents an alkyl group; the same applies hereinafter): Dialkyl peroxides such as diethyl peroxide (5) R—CO—O—O—CO—R type: peroxide Diacetyl, Diamyl peroxide, Acyl peroxide such as dibenzoyl peroxide, etc. (6) Peroxy acid type a) Acids having a —O—O— bond: Persulfuric acid (H ₂ SO ₅ ), Perphosphoric acid (H ₃ PO ₅ ) etc. b) R—CO—O—OH: performic acid, peracetic acid, perbenzoic acid, perphthalic acid, etc. (7) Hydrogen peroxide inclusions: (NaOOH) ₂ / H ₂ O ₂ , (KOOH) ₂ / 3H ₂ O _{2 and the} like Among these, hydrogen peroxide is particularly preferable because it can be easily decomposed later using a reducing agent, a reducing enzyme, or a catalyst.

The method for treating EVOH with a peroxide is not particularly limited, and a known treatment method can be used. Specifically, for example, a peroxide (eg, sometimes referred to as “EVOH solution”) in which EVOH is dissolved is added with a peroxide and a catalyst for molecular chain scission (eg, iron sulfate). And heating at 40 to 90 ° C. with stirring.

More specifically, in the case of using hydrogen peroxide as a peroxide, hydrogen peroxide (usually a 35 mass% aqueous solution) is added to a solution obtained by dissolving an EVOH solution in a solvent described later, and the mixture is stirred. Then, the treatment is performed under conditions of a temperature of 40 ° C. to 90 ° C. and 1 hour to 50 hours. The amount of hydrogen peroxide (35% by mass aqueous solution) added is about 3 to 300 parts by mass with respect to 100 parts by mass of EVOH in the solution. In addition, as a catalyst for molecular chain scission, a metal catalyst (CuCl ₂ , CuSO ₄ , MoO ₃ , FeSO ₄ , TiCl ₄ , SeO _2, etc.) is added at 1 ppm to EVOH solution in order to adjust the reaction rate of oxidative decomposition. You may add about 5000 ppm (mass standard, hereafter the same). The point at which the treatment is completed can be taken as a measure that the viscosity of the solution is about 10% or less of the initial value. By removing the solvent from the solution after the treatment by a known method, a terminal carboxylic acid-modified EVOH containing a carboxyl group of about 0.03 meq / g to 0.2 meq / g at the molecular end can be obtained. .

1-2. Inorganic layered compound Examples of the inorganic layered compound include clay minerals such as smectite, kaolin, mica, hydrotalcite, and chlorite. Specifically, montmorillonite, beidellite, saponite, hectorite, soconite, stevensite, kaolinite, nacrite, dickite, halloysite, hydrous halloysite, tetrasilic mica, sodium teniolite, muscovite, margarite, phlogopite, talc , Antigolite, chrysotile, pyrophyllite, vermiculite, xanthophyllite, chlorite and the like. Also, scaly silica can be used. These may be used alone or in combination of two or more. Among these, smectite (including synthetic products thereof) is particularly preferable.

Moreover, the thing in which the metal ion which has oxidation-reduction property in an inorganic layered compound, especially an iron ion exists is suitable. Further, among these, montmorillonite is preferably used from the viewpoint of coating suitability and gas barrier properties. As montmorillonite, known ones conventionally used for gas barrier agents can be used. For example, the general formula: (X, Y) _{2 to 3} Z ₄ O ₁₀ (OH) ₂ .mH ₂ O. (Wω) (wherein X represents Al, Fe (III), Cr (III). Y represents Mg, Fe (II), Mn (II), Ni, Zn, Li, Z represents Si, Al, W represents K, Na, Ca H ₂ O represents interlayer water M and ω represent positive real numbers). Among these, those in which W is Na are preferable from the viewpoint of cleavage in an aqueous medium. Further, the particle size of the inorganic layered compound is more preferably 5 μm or less, and the aspect ratio is preferably 50 to 5000, particularly 200 to 3000.

The content of the inorganic layered compound in the gas barrier resin composition (a total of 100% by weight of the gas barrier resin, the inorganic layered compound, and the additive) is 0.1% by weight or more, preferably 0.5% by weight or more. Preferably it is 1.0 mass% or more, More preferably, it is 1.2 mass% or more, 9.0 mass% or less, Preferably it is 7.0 mass% or less, More preferably, it is 6.0 mass% or less, More preferably It is 5.0 mass% or less. When the content of the inorganic layered compound is less than 0.1% by mass, the gas barrier property is lowered by retort treatment, or the laminate strength after retort treatment is lowered. On the other hand, when the content of the inorganic layered compound exceeds 9.0% by mass, the laminate strength and gas barrier properties are reduced by the retort treatment. This is because the delamination strength decreases due to the retort treatment, and peeling occurs between the inorganic thin film layer and the gas barrier resin layer, and the flexibility of the gas barrier resin layer decreases. It is presumed that the gas barrier property is lowered due to a crack in the gas barrier resin layer due to the stress of the shower water during the treatment.

Here, conventionally, it has been considered that when the amount of the inorganic stratiform compound in the gas barrier resin composition layer is small, the gas barrier property is low, and when it is large, the gas barrier property is high. However, in the case of laminating with an inorganic thin film layer as in the present invention, even if the content of the inorganic layered compound in the gas barrier resin composition layer is relatively small, a high gas barrier property is obtained due to a synergistic effect with the inorganic thin film. Show. This is because the gas barrier resin composition layer on the inorganic thin film layer not only fills in the defects caused by pinholes and cracks in the inorganic thin film, but also has the function of preventing damage such as cracking of the inorganic thin film, but contains an inorganic layered compound This is considered to be due to the fact that even if the amount is small, the function of filling the defects is sufficiently fulfilled. On the contrary, if the content of the inorganic layered compound increases, phenomena such as a decrease in interlayer adhesion during retort treatment and a decrease in film flexibility appear, and the function of preventing damage to the inorganic thin film decreases. It is considered that not only the improvement effect of the gas barrier property is not obtained, but also the gas barrier property is reduced.

The blending amount of the inorganic layered compound is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and 10 parts by mass or less with respect to 100 parts by mass of the gas barrier resin. More preferably, it is 9 mass parts or less, More preferably, it is 8 mass parts or less.

1-3. Additive In the present invention, the gas barrier resin composition contains at least one of a coupling agent and a crosslinking agent as an additive. The coupling agent is not particularly limited as long as it is used in a resin composition, but a silane coupling agent having at least one organic functional group is preferable. Examples of the organic functional group include an epoxy group, an amino group, an alkoxy group, and an isocyanate group.

Specific examples of the silane coupling agent having at least one organic functional group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 2-glycidyloxyethyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane Epoxy group-containing silane coupling agents such as 2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- [N- (2-aminoethyl) amino] ethyltrimeth Sisilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltriethoxysilane, 3- [N- (2-aminoethyl) amino ] Amino group-containing silane coupling agents such as propylmethyldimethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxy Alkoxy group-containing silane coupling agents such as silane, tetrapropoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane; γ-isocyanatopropyltrimethoxysila And isocyanate group-containing silane coupling agents such as γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and γ-isocyanatopropylmethyldiethoxysilane. These may be used alone or in combination of two or more.

The cross-linking agent is not particularly limited as long as it is used in a resin composition, but a cross-linking agent for a hydrogen bonding group is preferable. Examples of the hydrogen bonding group crosslinking agent include water-soluble zirconium compounds and water-soluble titanium compounds. Specific examples of water-soluble zirconium compounds include zirconium chloride, hydroxy zirconium chloride, basic zirconium sulfate, zirconium nitrate, ammonium zirconium carbonate, sodium zirconium sulfate, sodium zirconium citrate, zirconium lactate, zirconium acetate, zirconium sulfate, oxysulfuric acid Zirconium, zirconium oxynitrate, basic zirconium carbonate, zirconium hydroxide, potassium zirconium carbonate, zirconium chloride, zirconium chloride octahydrate, zirconium oxychloride, monohydroxytris (lactate) zirconium ammonium, tetrakis (lactate) zirconium ammonium, mono Examples thereof include hydroxytris (slate) zirconium ammonium. Among these, zirconium hydrochloride and hydroxyzirconium chloride are preferred from the viewpoint of hydrothermal treatment suitability after hydrothermal treatment by improving coating cohesion and the stability of the coating liquid for forming the gas barrier resin composition layer. In particular, zirconium hydroxide is preferred. Specific examples of water-soluble titanium compounds include titanium lactate, titanium lactate ammonium salt, diisopropoxy titanium (triethanolaminate), di-n-butoxytitanium bis (triethanolaminate), diisopropoxytitanium bis (triethanolaminate). Nate), titanium tetrakis (acetylacetonate) and the like. These may be used alone or in combination of two or more.

The content of the additive (coupling agent and crosslinking agent) in the gas barrier resin composition (a total of 100 mass% of the gas barrier resin, the inorganic layered compound, and the additive) is preferably 0.3 mass% or more. Preferably it is 0.5% by weight or more, more preferably 1% by weight or more, most preferably 8% by weight or more, preferably 20% by weight or less, more preferably 18% by weight or less, still more preferably 15% by weight or less, Most preferably, it is 12 mass% or less. By making content of an additive into the said range, the fall of the laminate strength after a retort process can be suppressed more.

Further, the blending amount of the additive is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 3 parts by mass or more, and 15 parts by mass with respect to 100 parts by mass of the gas barrier resin. The following is preferable, More preferably, it is 13 mass parts or less, More preferably, it is 12 mass parts or less.

1-4. Formation method As a method of forming the gas barrier resin composition layer on the inorganic thin film layer, for example, a coating liquid in which each material of the gas barrier resin composition is dissolved and dispersed in a solvent is applied on the inorganic thin film layer. Method: Method of melting gas barrier resin composition and extruding and laminating onto inorganic thin film layer; Method of separately forming a film of gas barrier resin composition and bonding this onto inorganic thin film layer with adhesive or the like; Etc. Among these, the method by coating is preferable from the viewpoints of simplicity and productivity. At this time, an anchor coat layer may be provided on the inorganic thin film layer, and a gas barrier resin composition layer may be provided on the anchor coat layer. The anchor coat layer will be described later.

Hereinafter, as an example of a method for forming the gas barrier resin composition layer, a method for applying a coating solution in which each material of the gas barrier resin composition is dissolved and dispersed in a solvent onto the inorganic thin film layer will be described.

As a solvent (solvent) for using the gas barrier resin composition as a coating liquid, either an aqueous or non-aqueous solvent capable of dissolving EVOH can be used, but a mixed solvent of water and a lower alcohol can be used. preferable. Specifically, water and lower alcohol having 2 to 4 carbon atoms (ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, n-butyl alcohol, iso-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, etc.) The mixed solvent is preferable. When such a mixed solvent is used, the solubility of EVOH becomes good and an appropriate solid content can be maintained. The content of the lower alcohol in the mixed solvent is preferably 15% by mass to 70% by mass. If the content of the lower alcohol in the mixed solvent is 70% by mass or less, when the inorganic layered compound is dispersed, the cleavage of the inorganic layered compound further proceeds, and if it is 15% by mass or more, the gas barrier resin composition The coating suitability of the coating solution in which the product is dissolved and dispersed is further improved.

A method for dissolving and dispersing the gas barrier resin composition in a solvent is not particularly limited. For example, an inorganic layered compound (if necessary, may be swollen and cleaved in a dispersion medium such as water in advance) in an EVOH solution. A method of dispersing and mixing an inorganic layered compound; adding EVOH (may be dissolved in a solvent in advance if necessary) to a dispersion obtained by swelling and cleaving the inorganic layered compound in a dispersion medium such as water The method of (dissolving) etc. is mentioned. At this time, the mass ratio between the gas barrier resin composed of EVOH and the inorganic layered compound is such that the content of the inorganic layered compound is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the gas barrier resin composition. Mix in the amount to be.

When mixing these, the inorganic layered compound can be uniformly dispersed using a normal stirring device or dispersing device. In particular, a high-pressure disperser is used to obtain a transparent and stable inorganic layered compound dispersion. can do. Examples of the high-pressure disperser include Gorin (manufactured by APV Gorin), Nanomizer (manufactured by Nanomizer), Microfluidizer (manufactured by Microflydex), Ultimizer (manufactured by Sugino Machine), DeBee (manufactured by Bee), etc. As a pressure condition of these high-pressure dispersers, it is preferable to perform the dispersion treatment at 100 MPa or less. When the pressure condition is 100 MPa or less, the pulverization of the inorganic layered compound can be suppressed, and the target gas barrier property is improved. The additive can be mixed only by stirring, so it can be added at any time, but it is added when the inorganic layered compound has been dispersed in the EVOH solution from the viewpoint of suppressing the influence of the additive as much as possible. It is preferable to add an agent. As the coating method, conventional methods such as gravure coating, bar coating, die coating and spray coating can be adopted according to the characteristics of the coating solution.

1-5. Drying conditions of gas barrier resin composition layer coating liquid The drying temperature after coating the gas barrier resin composition coating liquid is preferably 100 ° C or higher, more preferably 130 ° C or higher, and even more preferably 150 ° C. It is above and 200 degrees C or less is preferable. In addition, additional heat treatment in a separate processing step, that is, after the film is wound up once, while it is rolled back, or with a roll, or before or during the subsequent step such as a laminating step, additional heat treatment (150 to (200 ° C.) is also effective. When the drying temperature is 100 ° C. or higher, the coating layer can be sufficiently dried, crystallization and crosslinking of the gas barrier resin composition layer proceed, and the gas barrier property and laminate strength after retort treatment become better. On the other hand, if the drying temperature is 200 ° C. or lower, it is possible to prevent the plastic film from being overheated, to suppress the film from becoming brittle or to shrink, and to improve the workability.

1-6. The thickness of the gas barrier resin composition layer The thickness of the gas barrier resin composition layer is 0.05 μm or more, preferably 0.10 μm or more, more preferably 0.15 μm or more, and 0.5 μm or less, preferably 0. .3 μm or less, more preferably 0.2 μm or less. If the thickness is less than 0.05 μm, the gas barrier property after retort treatment is lowered. On the other hand, if the thickness exceeds 0.5 μm, the coating solution is insufficiently dried when the coating solution is used, resulting in a gas barrier resin composition. The material layer becomes brittle and the laminate strength after the retort treatment is lowered.

2. Plastic Film The plastic film used in the present invention is a film made of an organic polymer resin, which is stretched, cooled and heat-set in the longitudinal direction and / or the width direction as necessary after melt extrusion. Examples of the organic polymer include polyamide, polyester, polyolefin, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, wholly aromatic polyamide, polyamideimide, polyimide, polyetherimide, polysulfone, polystyrene, and polylactic acid. .

Specific examples of the polyamide include polycaproamide (nylon 6), poly-ε-aminoheptanoic acid (nylon 7), poly-ε-aminononanoic acid (nylon 9), polyundecanamide (nylon 11), polylaurin Lactam (nylon 12), polyethylenediamine adipamide (nylon 2.6), polytetramethylene adipamide (nylon 4.6), polyhexamethylene adipamide (nylon 6/6), polyhexamethylene sebacamide (Nylon 6 · 10), Polyhexamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene dodecamide (Nylon 6 · 12), Polyoctamethylene adipamide (Nylon 8.6), Polydecamethylene adipamide (Nylon 10.6), polydecamethylene sebacamide (nylon 10.10), poly Examples include lidodecamethylene dodecamide (nylon 12 and 12) and metaxylenediamine-6 nylon (MXD6). Copolymers based on these may also be used. Examples thereof include caprolactam / laurin lactam copolymer, caprolactam / hexamethylene diammonium adipate copolymer, laurin lactam / hexamethylene diammonium adipate copolymer. Polymer, hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer, ethylene diammonium adipate / hexamethylene diammonium adipate copolymer, caprolactam / hexamethylene diammonium adipate / hexamethylene diammonium sebacate copolymer Etc. It is also effective to blend these polyamides with plasticizers such as aromatic sulfonamides, p-hydroxybenzoic acid and esters, low elastic modulus elastomeric components and lactams as film flexibility modifying components. is there.

Specific examples of the polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, and the like. In addition, a copolymer containing these as a main component may be used. When a polyester copolymer is used, the dicarboxylic acid component includes terephthalic acid, isophthalic acid, phthalic acid, or 2,6-naphthalenedicarboxylic acid. Aromatic dicarboxylic acids; polyfunctional carboxylic acids such as trimellitic acid and pyromellitic acid; aliphatic dicarboxylic acids such as adipic acid and sebacic acid; Examples of the glycol component include aliphatic glycols such as ethylene glycol, 1,4-butanediol, diethylene glycol, propylene glycol and neopentyl glycol, aromatic glycols such as p-xylylene glycol; 1,4-cyclohexanedimethanol and the like And alicyclic glycols; polyethylene glycol having an average molecular weight of 150 to 20000; The ratio of the preferable copolymerization component in 100 mol% of polyester is 20 mol% or less. When the copolymerization component exceeds 20 mol%, film strength, transparency, heat resistance, etc. may be inferior. These organic polymers may be further copolymerized with a small amount of other monomers or blended with other organic polymers.

When the gas barrier laminate film of the present invention is used as a barrier film for solar cells, a barrier film for organic electroluminescence, or a barrier film for electronic paper, the organic polymer resin constituting the plastic film is polyethylene. Terephthalate or polyethylene naphthalate is preferred. In particular, when used as a barrier film for solar cells, it is desired that the hydrolysis resistance is high. Therefore, the acid value of the plastic film is preferably 10 equivalents / ton or less, more preferably 5 equivalents / ton or less. .

In addition, when polyethylene terephthalate is used, its intrinsic viscosity (IV value) is preferably 0.60 or more, more preferably 0.65 or more, preferably 0.90 or less, more preferably 0.80 or less. The IV value is a value measured at 30 ° C. in a mixed solvent of phenol / 1,1,2,2-tetrachloroethane (6/4 mass ratio). Moreover, 0.7 mass% or less is preferable, and, as for content of the cyclic trimer in polyethylene terephthalate, More preferably, it is 0.5 mass% or less.

The polycondensation catalyst for polyethylene terephthalate or polyethylene naphthalate is preferably a compound such as antimony, germanium, titanium, aluminum, or phosphorus. Among these, a polymerization catalyst composed of an aluminum compound and a phosphorus compound is preferable, and JP-A-2002-249565 Can be used. As the aluminum compound, aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum acetylacetonate and the like are preferable. The phosphorus compound is preferably a phosphonic acid compound having a hindered phenol structure, and specific examples include Irganox (registered trademark) 1222, 1425 (manufactured by Ciba Japan).

Furthermore, known additives such as an ultraviolet absorber, an antistatic agent, a plasticizer, a lubricant, a colorant, and the like may be added to the organic polymer resin. The thickness of the plastic film is preferably 1 μm or more, more preferably 2 μm or more, further preferably 3 μm or more, preferably 500 μm or less, more preferably 300 μm or less, and still more preferably 100 μm or less. The transparency of the plastic film is not particularly limited, but when used as a packaging material laminate having transparency, a film having a light transmittance of 50% or more is desirable. The plastic film may be a laminated film. There are no particular limitations on the type of laminate, the number of laminations, the lamination method, and the like in the case of a laminated film, and any one of known methods can be selected according to the purpose.

As for the plastic film production method, an existing method such as an extrusion method or a casting method can be used. The plastic film according to the present invention has a surface such as corona discharge treatment, glow discharge, flame treatment, surface roughening treatment, etc. prior to laminating the inorganic thin film layer as long as the object of the present invention is not impaired. Processing may be performed, and publicly known anchor coat processing, printing, and decoration may be performed.

3. Inorganic thin film layer The inorganic thin film layer is a thin film made of a metal or an inorganic oxide. The material for forming the metal thin film is not particularly limited as long as it can be formed into a thin film. Examples thereof include magnesium, aluminum, titanium, chromium, nickel, and indium. Aluminum is preferable from the viewpoint of cost and the like. The material for forming the inorganic oxide thin film is not particularly limited as long as it can be formed into a thin film, and examples thereof include silicon oxide, aluminum oxide, magnesium oxide, etc., preferably silicon oxide, aluminum oxide, magnesium oxide. is there. Among these, a multi-component inorganic oxide thin film containing silicon oxide and aluminum oxide is more preferable because of excellent gas barrier properties, and a silicon oxide / aluminum oxide binary inorganic oxide thin film is most preferable. The silicon oxide here is a mixture of various silicon oxides such as SiO and SiO ₂ , and the aluminum oxide is a mixture of various aluminum oxides such as AlO and Al ₂ O ₃ .

The reason why the multi-element inorganic oxide thin film containing silicon oxide and aluminum oxide is excellent in gas barrier property is that the multi-element inorganic oxide thin film changes the flexibility and gas barrier property of the film depending on the ratio of inorganic substances in the thin film. This is because it is possible to obtain a good thin film having a balanced performance. Moreover, when providing an adhesive bond layer on an inorganic thin film layer so that it may mention later, it is because high adhesive force is easy to be obtained between the multi-component system inorganic oxide thin film containing a silicon oxide and aluminum oxide, and an adhesive bond layer.

When the silicon oxide / aluminum oxide binary inorganic oxide thin film is used, the content of aluminum oxide in the inorganic oxide thin film is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass. % Or more, preferably 99% by mass or less, more preferably 75% by mass or less, and still more preferably 60% by mass or less. If the content of aluminum oxide in the silicon oxide / aluminum oxide binary inorganic oxide thin film is 20% by mass or more, the gas barrier property is further improved, and if it is 99% by mass or less, the flexibility of the deposited film is improved. It becomes good, it becomes strong to bending and dimensional change of the gas barrier laminate film, and the effect of the combination of the two is further improved.

Further, the relationship between the specific gravity value of the inorganic oxide thin film and the content (% by mass) of aluminum oxide in the inorganic oxide thin film is expressed as D = 0.01A + b (D: specific gravity of the thin film, A: aluminum oxide in the thin film) In the region where the b value is smaller than 1.6, the structure of the silicon oxide / aluminum oxide thin film becomes rough, and in the region where the b value is larger than 2.2, the oxidation Silicon / aluminum oxide binary inorganic oxide thin films tend to be hard.

Therefore, the specific gravity of the silicon oxide / aluminum oxide binary inorganic oxide thin film as the inorganic oxide thin film is such that the specific gravity of the thin film and the content (mass%) of aluminum oxide in the thin film D = 0.01A + b (D: The b value is preferably from 1.6 to 2.2, more preferably from 1.7 to 2.1, when expressed by the relational expression of specific gravity of the thin film, A: content of aluminum oxide in the thin film). However, of course, it is not limited to this range. A multi-component inorganic oxide thin film containing silicon oxide / aluminum oxide and further containing other inorganic oxides has a great effect as a gas barrier laminate.

In the present invention, the thickness of the inorganic thin film layer is preferably 1 nm or more, more preferably 5 nm or more, preferably 800 nm or less, and more preferably 500 nm or less. If the film thickness is 1 nm or more, the gas barrier property is further improved. In addition, even if it exceeds 800 nm too much, the effect of the gas barrier property equivalent to it is not acquired.

A method of forming the inorganic thin film layer will be described by taking a silicon oxide / aluminum oxide binary inorganic oxide thin film as an example. As a thin film forming method by a vapor deposition method, a vacuum vapor deposition method, a sputtering method, a physical vapor deposition method such as an ion plating method, a CVD method (chemical vapor deposition method), or the like is appropriately used. For example, when the vacuum deposition method is employed, a mixture of SiO ₂ and Al ₂ O ₃ or a mixture of SiO ₂ and Al is used as a deposition material. For heating, resistance heating, high-frequency induction heating, electron beam heating, etc. can be adopted, and oxygen, nitrogen, hydrogen, argon, carbon dioxide gas, water vapor, etc. are introduced as reaction gases, ozone addition, ion assist It is also possible to employ reactive vapor deposition using such means. Furthermore, the film forming conditions can be arbitrarily changed, such as applying a bias to the plastic film, heating or cooling the plastic film, and the like. The vapor deposition material, reaction gas, substrate bias, heating / cooling, and the like can be similarly changed when a sputtering method or a CVD method is employed. By such a method, a transparent and excellent gas barrier property is obtained, and a gas barrier laminate film having excellent performance capable of withstanding various treatments such as boiling treatment and retort treatment, and further gelbo test (flexibility test) is obtained. It becomes possible.

4). Anchor coat layer In the gas barrier laminate film of the present invention, it is preferable to have an anchor coat layer between the inorganic thin film layer and the gas barrier resin composition layer. By having an anchor coat layer, the adhesive force between the inorganic thin film layer and the gas barrier resin composition layer can be further improved.

The anchor coat layer is formed from an anchor coat layer composition containing an anchor coat agent resin composition and a solvent. Examples of the anchor coating agent resin composition include urethane-based, polyester-based, acrylic-based, titanium-based, isocyanate-based, imine-based, and polybutadiene-based resins, and epoxy-based, isocyanate-based, and melamine-based curing agents. Additions can be mentioned. Examples of the solvent (solvent) include aromatic solvents such as benzene and toluene; alcohol solvents such as methanol and ethanol; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as ethyl acetate and butyl acetate; Examples thereof include polyhydric alcohol derivatives such as glycol monomethyl ether.

The anchor coating agent resin composition preferably contains a silane coupling agent having at least one organic functional group. Examples of the organic functional group include an alkoxy group, an amino group, an epoxy group, and an isocyanate group. The addition amount of the silane coupling agent is preferably 0.1% by mass or more, more preferably 3% by mass in the anchor coating agent resin composition (total 100% by mass of resin, curing agent and silane coupling agent). It is above, 10 mass% or less is preferable, More preferably, it is 7 mass% or less. If the addition amount is 0.1% by mass or more, the laminate strength after the retort treatment is further improved.

The thickness of the anchor coat layer is preferably 0.05 μm or more, more preferably 0.10 μm or more, further preferably 0.15 μm or more, preferably 0.5 μm or less, more preferably 0.3 μm or less, still more preferably Is 0.25 μm or less. If the thickness of the anchor coat layer is 0.05 μm or more, a decrease in the laminate strength due to the retort treatment is further suppressed, and if it is 0.5 μm or less, coat spots do not occur and the gas barrier property becomes better.

5. Primer Coat Layer In the gas barrier laminate film of the present invention, a primer coat layer may be provided between the plastic film and the inorganic thin film layer. By having the primer coat layer, the planarity of the gas barrier laminate film can be improved, and the adhesive force between the plastic film and the inorganic thin film layer can be further improved.

The primer coat layer can be formed from a primer coat layer coating solution in which a resin component constituting the primer coat layer is dissolved or dispersed. Examples of the resin constituting the primer coat layer include a polyurethane resin and a copolyester resin. In particular, it is preferable to use a polyurethane resin and a copolyester resin together as the resin constituting the primer coat layer.

6). Lamination with other films, etc. The gas barrier laminate film of the present invention can be used for various applications including food packaging applications, and in addition, heat seal layers, printing layers, other resin films, these It can be laminated with other materials such as an adhesive layer for bonding the layers. When laminating, it is possible to employ known means such as a method of directly melt-extrusion laminating on the gas barrier laminate film of the present invention, a method of coating, a method of laminating films directly or via an adhesive. I can do it. When high barrier properties are required, two or more gas barrier laminate films of the present invention can be laminated.

For example, when used as a cover material for retort pouches or retort foods, it is preferable to provide a heat seal layer such as polyethylene or polypropylene on the gas barrier resin composition layer. Further, another resin film may be laminated between the gas barrier resin composition layer and the heat seal layer. As the other resin film, the resin film mentioned as a plastic film can be used. In the case of laminating these, they can be laminated via an adhesive.

When used for solar cells, the gas barrier laminate film of the present invention is laminated with a weather-resistant film such as a fluorine-based film or a hydrolysis-resistant polyester film, a light-reflective white film, a black colored film, or the like. Can be used as a back sheet. When used as a film on the light-receiving surface side of a solar cell, the gas barrier laminate film of the present invention is provided with an antifouling coat, a reflection reducing coat, an antiglare coat, a hard coat, etc., or other films with these coats applied. You may laminate. In the case of applications such as organic EL and electronic paper, an antifouling coat, a reflection reducing coat, an antiglare coat, a hard coat, etc. may be provided, or other films coated with these coats may be laminated. These other coats and other films may be provided on either side of the gas barrier laminate film of the present invention.

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention.

1. Evaluation method 1-1. Preparation of laminated gas barrier laminated film On the gas barrier resin composition layers 1 to 23 (an anchor coat layer in No. 16), an unstretched polypropylene film (“ P1147 ”(thickness 70 μm), manufactured by Toyobo Co., Ltd. was bonded and aged at 40 ° C. for 4 days to obtain a laminated gas barrier laminated film. The thickness of the adhesive layer after drying was 3 μm.

1-2. Water Vapor Permeability Measurement For laminated gas barrier laminated films, using a water vapor permeability measuring device ("PERMATRAN-W 3 / 33MG", manufactured by MOCON) according to JIS K7129 B method, the temperature is 40 ° C and the humidity is 100% RH. The water vapor permeability was measured under an atmosphere. The humidity control on the gas barrier laminate film was such that water vapor permeated from the plastic film side to the gas barrier resin composition layer side. In addition, the laminate gas barrier laminate film was subjected to a retort treatment at a temperature of 121 ° C. and an atmospheric pressure of 0.2 MPa (2 kgf / cm ² ) for 30 minutes and then dried at 40 ° C. for 1 day. Similarly, water vapor permeability was measured.

1-3. Oxygen permeability The laminated gas barrier laminate film was measured according to JIS K7126-1 (2006) Annex 1 using an oxygen permeability measuring device (“OX-TRAN 2/20”, manufactured by MOCON) at a temperature of 23 ° C. The oxygen permeability was measured in an atmosphere with a humidity of 65% RH. In addition, the laminate gas barrier laminate film was subjected to a retort treatment at a temperature of 121 ° C. and an atmospheric pressure of 0.2 MPa (2 kgf / cm ² ) for 30 minutes and then dried at 40 ° C. for 1 day. Similarly, the oxygen permeability was measured.

1-4. Laminate Strength Measurement Method Laminate gas barrier laminate film is cut into a width of 15mm and length of 200mm to make a test piece, and under the conditions of a temperature of 23 ° C and a relative humidity of 65%, Tensilon Universal Material Testing Machine ("Tensilon UMT-II-500 type" The laminate strength was measured using “Toyo Baldwin”. The tensile rate was 200 mm / min, and water was applied between the gas barrier laminate film and the unstretched polypropylene film, and the strength when peeled at a peel angle of 90 degrees was measured. In addition, the laminate gas barrier laminate film was subjected to a retort treatment at a temperature of 121 ° C. and an atmospheric pressure of 0.2 MPa (2 kgf / cm ² ) for 30 minutes and then dried at 40 ° C. for 1 day. Similarly, the laminate strength was measured.

1-5. Gas Barrier Resin Composition Layer Thickness A gas barrier laminate film sample was cut into a 2 mm × 5 mm strip and embedded in an epoxy resin. The embedded sample was made into an ultrathin section with a microtome and stained with ruthenium tetroxide as a staining agent. For observation, a transmission electron microscope (“JEM2100” manufactured by JEOL Ltd.) was used, and the acceleration voltage was 200 kV, the observation magnification was 5,000 times, and 10,000 times. The thickness of the gas barrier resin composition layer Was measured.

2. Preparation 2-1. Production of plastic film Intrinsic viscosity 0.62 (30 ° C., phenol / tetrachloroethane (mass ratio) = 60/40), polyethylene terephthalate (PET) containing 100 ppm of silica is pre-crystallized, and then this is dried and has a T-die Extrusion was performed at 280 ° C. using an extruder, and rapidly cooled and solidified on a drum having a surface temperature of 40 ° C. to obtain an amorphous sheet. Next, the obtained sheet was stretched 4 times at 100 ° C. in the longitudinal direction between a heating roll and a cooling roll to obtain a uniaxially stretched PET film.

2-2. Preparation of coating solution for forming anchor coat layer <Preparation Example 1>
An isocyanate-based curing agent (Takelac A-50, manufactured by Mitsui Chemicals) is added to a urethane-based resin (Takelac (registered trademark) A525-S, manufactured by Mitsui Chemicals), and ethyl acetate is added to the solvent. The solid content concentration was adjusted to 6.5% by mass. Here, an epoxy-based silane coupling agent (“KBM403”, manufactured by Shin-Etsu Chemical Co., Ltd.) is contained in an anchor coating agent resin composition (100% by mass in total of resin, curing agent and silane coupling agent). It is added so that it becomes mass%, and the coating liquid No. It was set to 1.

<Preparation Example 2>
An anchor coat layer solution coating solution No. 1 was prepared in the same manner as in Preparation Example 1 except that the silane coupling agent was changed to an isocyanate-based silane coupling agent (“KBE9007”, manufactured by Shin-Etsu Chemical Co., Ltd.). 2 was prepared.

<Preparation Example 3>
The anchor coat layer solution coating solution No. 1 was prepared in the same manner as in Preparation Example 1 except that the silane coupling agent was changed to an amine-based silane coupling agent (“KBM603”, manufactured by Shin-Etsu Chemical Co., Ltd.). 3 was prepared.

<Preparation Example 4>
Preparation Example 1 except that the resin was changed to a urethane-based resin (“EL-530A”, manufactured by Toyo Morton), and the curing agent was changed to an isocyanate-based curing agent (“EL-530B”, manufactured by Toyo Morton). Similarly, the coating liquid for anchor coat layer No. 4 was prepared.

<Preparation Example 5>
An isocyanate-based curing agent (Takelac A-50, manufactured by Mitsui Chemicals) is added to a urethane-based resin (Takelac (registered trademark) A525-S, manufactured by Mitsui Chemicals), and ethyl acetate is added to the solvent. The solid content concentration was adjusted to 6.5% by mass, and this was prepared as anchor coat layer coating liquid No. It was set to 5.

2-3. Preparation of material for gas barrier resin composition layer <Preparation of ethylene-vinyl alcohol copolymer solution>
An ethylene-vinyl alcohol copolymer (trade name: “SG-525” (saponified ethylene-vinyl acetate copolymer) was added to a mixed solvent of 20.996 parts by mass of purified water and 51 parts by mass of n-propyl alcohol (NPA). 15 parts by mass of an obtained polymer, an ethylene ratio of 26 mol%, a degree of saponification of vinyl acetate component of about 100%, and a product of Nippon Synthetic Chemical Co., Ltd. (hereinafter sometimes abbreviated as “EVOH”). Further, 13 parts by mass of hydrogen peroxide (concentration: 30% by mass) and 0.004 parts by mass of iron sulfate (FeSO ₄ ) were added, heated to 80 ° C. with stirring, and reacted for about 2 hours. Thereafter, the mixture was cooled and catalase was added to 3000 ppm to remove residual hydrogen peroxide, whereby an almost transparent ethylene-vinyl alcohol copolymer solution (EVOH solution) having a solid content of 15% by mass was obtained.

<Preparation of polyvinyl alcohol resin solution>
To 70 parts by mass of a mixed solvent composed of 40% by mass of purified water and 60% by mass of n-propyl alcohol (NPA), a completely saponified polyvinyl alcohol resin (trade name: “GOHSENOL® NL-05” (degree of saponification 99.5). %) Or more, and 30 parts by mass of Nippon Synthetic Chemical Co., Ltd. were added and dissolved to obtain a transparent polyvinyl alcohol solution having a solid content of 30% by mass.

<Preparation of inorganic layered compound dispersion>
4 parts by mass of montmorillonite (trade name: “Kunipia (registered trademark) F”, manufactured by Kunimine Kogyo Co., Ltd.), which is an inorganic layered compound, was added to 96 parts by mass of purified water while stirring, and the pressure was set to 50 MPa with a high-pressure dispersing device. And fully dispersed. Thereafter, the mixture was kept at 40 ° C. for 1 day to obtain an inorganic layered compound dispersion having a solid content of 4% by mass.

<Additives>
Cross-linking agent: zirconium hydrochloride (trade name “Zircosol (registered trademark) Zc-20” (solid content 20% by mass), manufactured by Daiichi Rare Elemental Chemical Co., Ltd.)
Cross-linking agent: Titanium lactate (trade name: “Orgatyx (registered trademark) TC-310” (solid content: about 45% by mass), manufactured by Matsumoto Pharmaceutical Co., Ltd.)
Silane coupling agent: 3-glycidoxypropyltriethoxysilane (trade name: “KBE-403” (solid content: 100% by mass), manufactured by Shin-Etsu Chemical Co., Ltd.)

2-4. Preparation of coating liquid for forming gas barrier resin composition layer <Preparation Example 1>
31.75 parts by mass of the EVOH solution was added to 62.30 parts by mass of the mixed solvent A (purified water: n-propyl alcohol (mass ratio) = 40: 60), and the mixture was sufficiently stirred and mixed. Further, 5.95 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After adding 3 parts by mass of a cation exchange resin to 100 parts by mass of this dispersion and stirring for 1 hour at a stirring speed at which the ion exchange resin is not crushed to remove cations, Only the cation exchange resin was filtered off with a strainer.
The dispersion obtained by the above operation was further subjected to dispersion treatment at a pressure of 50 MPa using a high-pressure dispersion apparatus. To 97 parts by mass of the dispersed liquid mixture, 0.75 parts by mass of zirconium chloride as an additive, 0.9 parts by mass of purified water, and 1.35 parts by mass of NPA are added and stirred, and the resulting mixture is 255 mesh. It filtered with the filter (mesh 60 micrometers), and coating liquid No. for gas barrier resin composition layer formation with a solid content of 5 mass%. 1 was obtained.

<Preparation Example 2>
Prepared except that mixed solvent A, EVOH solution and inorganic layered compound dispersion were changed to 65.76 parts by weight of mixed solvent A, 33.00 parts by weight of EVOH solution, and 1.24 parts by weight of inorganic layered compound dispersion. In the same manner as in Example 1, the gas barrier resin composition layer forming coating solution No. 5 having a solid content of 5% by mass was prepared. 2 was obtained.

<Preparation Example 3>
Prepared except that mixed solvent A, EVOH solution and inorganic layered compound dispersion were changed to 64.00 parts by weight of mixed solvent A, 32.36 parts by weight of EVOH solution, and 3.64 parts by weight of inorganic layered compound dispersion. In the same manner as in Example 1, the gas barrier resin composition layer forming coating solution No. 5 having a solid content of 5% by mass was prepared. 3 was obtained.

<Preparation Example 4>
Prepared except that mixed solvent A, EVOH solution and inorganic layered compound dispersion were changed to 66.21 parts by weight of mixed solvent A, 33.17 parts by weight of EVOH solution, and 0.62 parts by weight of inorganic layered compound dispersion. In the same manner as in Example 1, the gas barrier resin composition layer forming coating solution No. 5 having a solid content of 5% by mass was prepared. 4 was obtained.

<Preparation Example 5>
Prepared except that mixed solvent A, EVOH solution and inorganic layered compound dispersion were used in amounts changed to mixed solvent A 60.67 parts by weight, EVOH solution 31.15 parts by weight, inorganic layered compound dispersion 8.18 parts by weight In the same manner as in Example 1, the gas barrier resin composition layer forming coating solution No. 5 having a solid content of 5% by mass was prepared. 5 was obtained.

<Preparation Example 6>
Preparation Example 1 except that the additive was changed to 0.15 parts by mass of 3-glycidoxypropyltriethoxysilane, and the amounts of purified water and NPA used were changed to 1.14 parts by mass of purified water and 1.71 parts by mass of NPA. In the same manner as described above, the gas barrier resin composition layer-forming coating solution No. 5 having a solid content of 5 mass% was used. 6 was obtained.

<Preparation Example 7>
In the same manner as in Preparation Example 1 except that the additive was changed to 0.33 parts by mass of titanium lactate, and the amounts of purified water and NPA used were changed to 1.07 parts by mass of purified water and 1.60 parts by mass of NPA. 5% by mass of gas barrier resin composition layer forming coating solution No. 7 was obtained.

<Preparation Example 8>
Prepared except that mixed solvent A, EVOH solution and inorganic layered compound dispersion were used in the amount of 59.10 parts by weight of mixed solvent A, 30.58 parts by weight of EVOH solution, and 10.32 parts by weight of inorganic layered compound dispersion. In the same manner as in Example 1, the gas barrier resin composition layer forming coating solution No. 5 having a solid content of 5% by mass was prepared. 8 was obtained.

<Preparation Example 9>
32.40 parts by mass of the EVOH solution was added to 61.52 parts by mass of the mixed solvent A, and the mixture was sufficiently stirred and mixed. Further, 6.08 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After adding 3 parts by mass of a cation exchange resin to 100 parts by mass of this dispersion and stirring for 1 hour at a stirring speed that does not cause crushing of the ion exchange resin, the cation is removed. Only the ion exchange resin was filtered off with a strainer.
The dispersion obtained by the above operation was further subjected to a dispersion treatment with a high-pressure dispersion apparatus at a pressure of 50 MPa, and then 0.25 part by mass of zirconium hydrochloride with respect to 97 parts by mass of the mixture subjected to the dispersion treatment, and a mixed solvent A 2.75 parts by mass of A was added and mixed and stirred. The mixture was filtered through a 255 mesh filter, and the coating liquid No. A for forming a gas barrier resin composition layer having a solid content of 5% by mass was used. 9 was obtained.

<Preparation Example 10>
29.46 parts by mass of the EVOH solution was added to 65.02 parts by mass of the mixed solvent A, and the mixture was sufficiently stirred and mixed. Further, 5.52 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After adding 3 parts by mass of a cation exchange resin to 100 parts by mass of this dispersion and stirring for 1 hour at a stirring speed that does not cause crushing of the ion exchange resin, the cation is removed. Only the ion exchange resin was filtered off with a strainer.
The dispersion obtained by the above operation was further subjected to dispersion treatment at a pressure of 50 MPa with a high-pressure dispersion apparatus, and then 2.50 parts by mass of zirconium hydrochloride with respect to 97 parts by mass of the dispersion treated, mixed solvent A 0.50 part by mass of A was added and mixed and stirred. The mixture was filtered through a 255 mesh filter, and the coating liquid No. 10 was obtained.

<Preparation Example 11> (No inorganic layered compound)
33.33 parts by mass of the EVOH solution was added to 66.67 parts by mass of the mixed solvent A, and the mixture was sufficiently stirred and mixed. Further, after adding 3 parts by mass of a cation exchange resin to 100 parts by mass of this solution and stirring for 1 hour at a stirring speed that does not cause crushing of the ion exchange resin, the cation is removed. Only the cation exchange resin was filtered off with a strainer.
To 97 parts by mass of the mixed liquid thus obtained, 0.75 part by mass of zirconium hydroxide and 2.25 parts by mass of mixed solvent A were added and mixed and stirred, and this was filtered with a 255 mesh filter. Filtration and coating liquid No. 5 for forming a gas barrier resin composition layer having a solid content of 5% by mass 11 was obtained.

<Preparation Example 12> (Using polyvinyl alcohol resin)
15.87 parts by mass of the polyvinyl alcohol resin solution was added to 78.17 parts by mass of the mixed solvent A, and the mixture was sufficiently stirred and mixed. Further, 5.95 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After adding 3 parts by mass of a cation exchange resin to 100 parts by mass of this dispersion and stirring for 1 hour at a stirring speed that does not cause crushing of the ion exchange resin, the cation is removed. Only the ion exchange resin was filtered off with a strainer.
The dispersion obtained by the above operation was further subjected to a dispersion treatment with a high-pressure dispersion apparatus at a pressure of 50 MPa, and then 0.75 part by mass of zirconium hydrochloride with respect to 97 parts by mass of the dispersion-treated mixture, A2.25 parts by mass were added, mixed and stirred, filtered through a 255 mesh filter and coated with a gas barrier resin composition layer forming solution No. 5 having a solid content of 5% by mass. 12 was obtained.

<Preparation Example 13> (No additive)
31.75 parts by mass of the EVOH solution was added to 62.30 parts by mass of the mixed solvent A, and the mixture was sufficiently stirred and mixed. Further, 5.95 parts by mass of the inorganic layered compound dispersion was added to this solution while stirring at high speed. After adding 3 parts by mass of a cation exchange resin to 100 parts by mass of this dispersion and stirring for 1 hour at a stirring speed that does not cause crushing of the ion exchange resin, the cation is removed. Only the ion exchange resin was filtered off with a strainer.
The dispersion obtained from the above operation is further subjected to dispersion treatment at a pressure of 50 MPa with a high-pressure dispersion apparatus, and then filtered through a 255 mesh filter to form a gas barrier resin composition layer having a solid content of 5% by mass. Coating liquid No. 13 was obtained.

3. Production of gas barrier laminate film <Production Example 1>
The uniaxially stretched PET film obtained above was stretched 4.0 times in the transverse direction at a temperature of 120 ° C., and while performing relaxation in the transverse direction of 6%, the temperature of the heat setting zone was set at 225 ° C. went. The treatment time at each temperature was 3 seconds at a preheating temperature of 100 ° C., 5 seconds at a stretching temperature of 120 ° C., and 8 seconds at a heat fixing treatment temperature of 225 ° C. After cooling, both edges were cut and removed to continuously form a biaxially stretched PET film having a thickness of 12 μm over 1000 m to produce a mill roll. The obtained mill roll was slit into a width of 400 mm and a length of 1000 m, and wound on a 3-inch paper tube to obtain a PET film. A binary inorganic oxide thin film layer of silicon oxide and aluminum oxide (ratio of silicon oxide / aluminum oxide (mass ratio) = 60/40) was formed as an inorganic thin film layer on the PET film.

Here, the inorganic thin film layer uses, as a deposition source, particulate SiO ₂ (purity 99.99%) and A1 ₂ O ₃ (purity 99.9%) having a size of about 3 mm to 5 mm, and electron beam deposition. By the method, a binary inorganic oxide thin film of aluminum oxide and silicon dioxide was formed. The vapor deposition material was divided into two without being mixed. An EB (Electron Beam) gun was used as a heating source, and each of A1 ₂ O ₃ and SiO ₂ was heated in a time-sharing manner. Each material was heated so that the emission current of the EB gun at that time was 1.2 A and the mass ratio of A1 ₂ O ₃ and SiO ₂ was 40:60. The film feed rate was 30 m / min, and the pressure during vapor deposition was adjusted to 1 × 10 ⁻² Pa. The temperature of the roll for cooling the film during vapor deposition was adjusted to -10 ° C. The thickness of the inorganic thin film layer thus obtained was 27 nm.

Coating solution No. for anchor coat layer on the inorganic thin film layer 1 was applied by a gravure roll coat method and dried to form an anchor coat layer. The thickness of the anchor coat layer after drying was 0.30 μm. On the anchor coat layer, gas barrier resin composition layer forming coating solution No. 1 was applied by a gravure roll coating method and dried at 160 ° C. to form a gas barrier resin composition layer. 1 was produced. The thickness of the gas barrier resin composition layer after drying was 0.25 μm.

<Production Examples 2 to 10>
The gas barrier resin composition layer forming coating solution is referred to as gas barrier resin composition layer forming coating solution no. The gas barrier laminate film No. 1 was prepared in the same manner as in Production Example 1 except that it was changed to 2-10. 2 to 10 were produced.

<Production Example 11>
Except that the mass ratio of silicon oxide to aluminum oxide (silicon oxide / aluminum oxide) in the binary oxide inorganic thin film layer of silicon oxide and aluminum oxide was changed to 50/50, the same as in Production Example 1, Gas barrier laminate film No. 11 was produced.

<Production Examples 12 to 15>
The coating liquid for anchor coat layer was applied as coating liquid No. for anchor coat layer. Except for the change to 2-5, the gas barrier laminate film No. 12 to 15 were produced.

<Production Example 16>
A gas barrier laminate film No. 1 was prepared in the same manner as in Production Example 1 except that the gas barrier resin composition layer was not formed. 16 was produced.

<Production Example 17>
A gas barrier laminate film No. 1 was prepared in the same manner as in Production Example 1 except that the inorganic thin film layer was not formed. 17 was produced.

<Production Examples 18 to 20>
The gas barrier resin composition layer forming coating solution is referred to as gas barrier resin composition layer forming coating solution no. A gas barrier laminate film No. 1 was prepared in the same manner as in Production Example 1 except that it was changed to 11-13. 18-20 were produced.

<Production Example 21>
In the same manner as in Production Example 1, except that the thickness of the gas barrier resin composition layer was changed to 0.01 μm, the gas barrier laminate film No. 21 was produced.

<Production Example 22>
A gas barrier laminate film No. 1 was prepared in the same manner as in Production Example 1 except that the thickness of the anchor coat layer was changed to 0.01 μm. 22 was produced.

<Production Example 23>
In the same manner as in Production Example 1, except that the thickness of the gas barrier resin composition layer was changed to 0.7 μm, the gas barrier laminate film No. 23 was produced.

The produced gas barrier laminate film No. Tables 1 and 2 show the configurations 1 to 23 and the evaluation results thereof.

Gas barrier laminated film No. 1 to 15 and 22 satisfy the requirements of the present invention. These films have high laminate strength and low oxygen permeability and water vapor permeability even after retorting. Among these, the gas barrier laminate film No. 1 having an anchor coat layer having a thickness of 0.3 μm between the inorganic thin film layer and the gas barrier resin composition layer. In Nos. 1 to 15, the laminate strength after the retort treatment was more excellent.

Gas barrier laminated film No. No. 16 does not have a gas barrier resin composition layer. No. 17 has no inorganic thin film layer. Although 18 is a case where a gas barrier resin composition does not contain an inorganic layered compound, these are values with high oxygen permeability and water vapor permeability.

Gas barrier laminated film No. Although 19 is a case where PVA is used as a gas barrier resin, the gas barrier laminate film and the unstretched polypropylene film were peeled off during the retort treatment. Gas barrier laminate film No. No. 20 is a case where the gas barrier resin composition does not contain an additive. This showed high values of oxygen permeability and water vapor permeability before retort treatment, and the laminate strength was very weak.

Gas barrier laminated film No. 21 is the case where the thickness of the gas barrier resin composition layer is less than 0.05 μm, but the oxygen permeability after the retort treatment was increased. That is, the gas barrier property after the retort treatment was lowered. Gas barrier laminate film No. No. 23 is a case where the thickness of the gas barrier resin composition layer exceeds 0.5 μm, but the laminate strength after the retort treatment was very weak.

According to the present invention, it is possible to obtain a gas barrier laminate film having a high gas barrier property against oxygen, water vapor and the like, and having a high interlayer adhesion and an excellent laminate strength. In particular, even if a retort treatment is performed, the gas barrier property and interlayer adhesive force are hardly lowered, and a highly practical gas barrier laminate film suitable for various applications can be obtained. Moreover, it becomes the gas barrier laminated film which is excellent in production stability and is easy to obtain uniform characteristics.

The gas barrier film of the present invention is not limited to food packaging for retorts, but is used for packaging of various foods, pharmaceuticals, and industrial products, and is required to be placed in a high-temperature and high-humidity environment and have long-term stable gas barrier properties and durability. It can be widely used for industrial applications such as solar cells, electronic paper, organic EL elements, and semiconductor elements.

Claims

An inorganic thin film layer and a gas barrier resin composition layer are laminated in this order with or without other layers on at least one surface of the plastic film,
The gas barrier resin composition layer is formed from a gas barrier resin composition comprising a gas barrier resin comprising an ethylene-vinyl alcohol copolymer, an inorganic layered compound, and an additive,
The content of the inorganic layered compound in the gas barrier resin composition is 0.1% by mass to 9.0% by mass, and the additive is a coupling agent and / or a crosslinking agent,
A gas barrier laminate film, wherein the gas barrier resin composition layer has a thickness of 0.05 μm to 0.5 μm.
The gas barrier laminate film according to claim 1, wherein the inorganic layered compound is smectite.
The gas barrier laminate film according to claim 1 or 2, wherein the coupling agent is a silane coupling agent having at least one organic functional group.
The gas barrier laminate film according to any one of claims 1 to 3, which contains a hydrogen bonding group crosslinking agent as the crosslinking agent.
The gas barrier property according to any one of claims 1 to 4, wherein a total content of additives (coupling agent and / or crosslinking agent) in the gas barrier resin composition is 0.3% by mass to 20% by mass. Laminated film.
The gas barrier laminate film according to any one of claims 1 to 5, wherein the inorganic thin film layer contains at least an inorganic oxide.
The gas barrier laminate film according to any one of claims 1 to 6, further comprising an anchor coat layer having a thickness of 0.05 to 0.5 µm between the inorganic thin film layer and the gas barrier resin composition layer.
The gas barrier laminate film according to claim 7, wherein the anchor coat agent resin composition for forming the anchor coat layer contains a silane coupling agent having at least one organic functional group.
The gas barrier laminate film according to claim 8, wherein the addition amount of the silane coupling agent in the anchor coat agent resin composition for forming the anchor coat layer is 0.1 mass% to 10 mass%.